Fluorine-containing polymer

ABSTRACT

A fluorine-containing polymer comprising units of the formula: ##STR1## wherein R 1  and R 2  are, the same or different, a fluorine-containing organic group, R 3  and R 4  are, the same and different, hydrogen or a lower acyl group, and Q 1  and Q 2  are, the same or different, a divalent organic group with at least one oxy group, which polymer having a number average molecular weight of 5,000 to 100,000, which is easily dissolved in oils and lowers surface tension thereof.

BACKGROUND OF THE INVENTION

The present invention relates to a fluorine-containing polymer. Moreparticularly, the present invention relates to a fluorine-containingpolymer derived from a fluorine-containing diamine and a diepoxide.

SUMMARY OF THE INVENTION

One object of the present invention is to provide a novelfluorine-containing polymer comprising units derived from afluorine-containing diamine and a diepoxide.

Another object of the present invention is to provide a novelfluorine-containing polymer which is easily soluble in oils and lowersthe surface tension thereof.

A further object of the present invention is to provide a novelfluorine-containing polymer which is useful as an additive, a levelingagent, an emulsifier, etc.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a fluorine-containing polymer comprisingunits of the formula: ##STR2## wherein R¹ and R² are, the same ordifferent, a fluorine-containing organic group, R³ and R⁴ are, the sameand different, hydrogen or a lower acyl group, and Q¹ and Q² are, thesame or different, a divalent organic group with at least one oxy group.The polymer has a number average molecular weight of 5,000 to 100,000.

In the formula (I), R¹ and R² are each a fluorine-containing organicgroup, preferably a group of the formula:

    R.sub.f (CH.sub.2).sub.n Y.sub.k --                        (II)

wherein R_(f) is a C₃ -C₂₁ fluorine-containing aliphatic group which maycontain at least one oxy group, Y is a group of the formula: ##STR3##wherein R³ is the same as described above, n is an integer of 0 to 8 andk is 0 or 1.

The lower acyl group of R³ and R⁴ is one having one to four carbonatoms.

Q¹ and Q² are each a divalent organic group with at least one oxy group,and preferably a C₃ -C₁₂₀ oxyalkylene group optionally having a hydroxylgroup, or a group of the formula: ##STR4## wherein R⁵ is a C₃ -C₁₂₀alkylene group optionally having an oxy group or a C₆ -C₁₅ aromaticgroup, and m is an integer of 1 to 8.

The fluorine-containing polymer of the present invention may be preparedby polymerizing a diamine of the formula: ##STR5## wherein R¹, R² and Q¹are the same as defined above and a diepoxide of the formula: ##STR6##wherein Q² is the same as defined above in an organic solvent.

Specific examples of the organic solvent are alcohols (e.g. methanol,ethanol, isopropanol, butanol, etc.), ethers (e.g. diethyl ether,tetrahydrofuran, monglyme, diglyme, etc.), hydrocarbons (e.g. hexane,heptane, etc.) and aromatic compounds (e.g. benzene, toluene, etc.).

The reaction temperature is preferably from 20° to 150° C., and morepreferably from 60° to 100° C. The reaction time is preferably from 3 to10 hours, more preferably from 5 to 8 hours.

The reaction of the diamine compound (V) and the diepoxide (VI) proceedswith the ring opening of the epoxy groups of the diepoxide (VI) andforming hydroxyl groups. The thus formed hydroxyl groups may be acylatedso as to improve solubility of the polymer in oils. The acylation may becarried out by a per se conventional method, for example, with acorresponding acid halide or anhydride.

Specific examples of the diamine (V) are as follows: ##STR7##

Specific examples of the diepoxide (VI) are as follows: ##STR8##

The fluorine-containing polymer of the present invention has somecharacteristics which are not found in similar conventional polymers.For example, the polymer is well dissolved in oils and lowers thesurface tension of the oils. A lubricant has better lubricity as it moreeasily forms a thin homogeneous film when it is applied on a slidingsurface of, for example, metal. For the formation of such a film, thelubricant should have smaller surface tension. When the polymer of theinvention is added to the lubricant even in a small amount, iteffectively lowers the surface tension.

In addition to the above application as an additive for the oils, thefluorine-containing polymer of the present invention is preferably usedas an additive for a fire-extinguisher, a leveling agent for variouswaxes and coatings, a penetrating agent for fibers, metals or photographprocessing agent, a surface-modifying agent for resins, a mold releaseagent, and an emulsifier for emulsion polymerization.

The present invention will be hereinafter explained further in detail byfollowing Examples.

EXAMPLE 1

To a four-necked 100 ml flask, added were C₉ F₁₉ CH₂ CH(OH)CH₂ NH(CH₂)₃O[(CH₂)₄ O]₈ (CH₂)₃ NHCH₂ CH(OH)CH₂ C₉ F₁₉ (17.6 g, 0.01 mole, ##STR9##(6.14 g, 0.01 mole) and isopropanol (20 g) and reacted at 80° C. for 6hours with stirring. Thereafter, isopropanol was distilled from thereaction mixture under reduced pressure. The residue was washed withbenzene and dried under reduced pressure to obtain a viscous liquid(21.5 g).

A number average molecular weight (M_(n)) and its degree of distribution(M_(w) /M_(n)) of the thus prepared liquid were measured by means of agel permeation chromatography (manufactured by Waters) under followingconditions to be 1.3×10⁴ and 1.4, respectively.

Conditions

Column: connected columns of Shodex (trade name) A-803, A-805 and A-806

Standard: polystyrene

Solvent: dimethylformamide

Temperature: 40° C.

Flow rate: 1.0 ml/min.

Sample concentration: 0.1% by weight.

In IR spectrum, absorption at 1,250 cm⁻¹ corresponding to symmetricstretching vibration of the epoxy rings and that at 3,330 cm⁻¹corresponding to stretching vibration of the nitrogen-hydrogen bonds inthe secondary amine disappeared. In ¹ H-NMR, a signal at δ=4.65 ppm forhydrogen atoms of the secondary amine disappeared and that at δ=4.83 ppmfor hydrogen atoms of the hydroxyl groups appeared.

    ______________________________________                                        Elemental analysis:                                                                          C      H         N    F                                        ______________________________________                                        Calc'd (%):    45.49  6.07      1.18 30.41                                    Found (%):     45.61  6.05      1.10 30.21                                    ______________________________________                                    

According to the above results, the product was identified as a compoundhaving repeating units of the formula: ##STR10##

EXAMPLE 2

In the same manner as in Example 1 but using, as starting materials, C₈F₁₇ CH₂ CH₂ NH(CH₂)₃ O(CH₂ CH₂ O)₂ (CH₂)₃ NHCH₂ CH₂ C₈ F₁₇ (13.68 g,0.01 mole) and ##STR11## (2.78 g, 0.01 mole), the reaction was carriedout to obtain a viscous liquid (14.70 g). M_(n) =1.3×10⁴. M_(w) /M_(n)=1.5.

The results of IR and NMR analyses were substantially the same as thosein Example 1.

    ______________________________________                                        Elemental analysis:                                                                          C      H         N    F                                        ______________________________________                                        Calc'd (%):    37.99  3.17      2.01 46.47                                    Found (%):     37.68  3.05      2.22 46.40                                    ______________________________________                                    

The product was identified as a compound having repeating units of theformula: ##STR12##

EXAMPLE 3

In the same manner as in Example 1 but using, as starting materials, C₉F₁₉ CH₂ CH(OH)CH₂ NHCH₂ CH(CH₃)CH₂ O[CH(CH₃)CH₂ O]₂ CH(CH₃)CH₂ NHCH₂CH(OH)CH₂ C₉ F₁₉ (13.0 g, 0.01 mole) and ##STR13## (2.04 g, 0.01 mole),the reaction was carried out to obtain a highly viscous liquid (13.79g). M_(n) =1.1×10⁴. M_(w) /M_(n) =1.3.

The results of IR and NMR analyses were substantially the same as thosein Example 1.

    ______________________________________                                        Elemental analysis:                                                                          C      H         N    F                                        ______________________________________                                        Calc'd:        35.90  3.59      1.86 48.01                                    Found:         36.08  3.71      1.81 47.77                                    ______________________________________                                    

The product was identified to be a compound having repeating units ofthe formula: ##STR14##

EXAMPLES 4 TO 8 AND COMPARATIVE EXAMPLES 1 TO 3

The surface tension of a 4% by weight solution of the following polymerof a low molecular weight compound in a lubricant (Susony 4GSmanufactured by Sunoil Co., Ltd.) was measured by Wilhelmy's method at25° C.

EXAMPLE 4

Copolymer of ##STR15## M_(n) =1.4×10⁴.

EXAMPLE 5

Copolymer of ##STR16## M_(n) =1.3×10⁴.

EXAMPLE 6

Copolymer of ##STR17## M_(n) =1.8×10⁴.

EXAMPLE 7

Copolymer of ##STR18## M_(n) =1.1×10⁴.

EXAMPLE 8

Copolymer of ##STR19## M_(n) =1.8×10⁴.

COMPARATIVE EXAMPLE 1

Copolymer of ##STR20## molar ratio of 1:2. M_(n) =2.0×10⁴. M_(w) /M_(n)=3.0.

COMPARATIVE EXAMPLE 2 ##STR21## COMPARATIVE EXAMPLE 3 ##STR22##

Resultant surface tension is shown in the Table.

                  TABLE                                                           ______________________________________                                                        Surface tension                                                               (dyn/cm)                                                      ______________________________________                                        Example 4         12.0                                                        Example 5         11.8                                                        Example 5         10.7                                                        Example 7         12.2                                                        Example 8         11.1                                                        Comparative Example 1                                                                           18.0                                                        Comparative Example 2                                                                           29.8                                                        Comparative Example 3                                                                           23.0                                                        (No additive)     31.1                                                        ______________________________________                                    

EXAMPLE 9 AND COMPARATIVE EXAMPLE 4

To a composition of Susony 4GS (80% by weight) and a polymer ofchlorotrifluoroethylene with a number average molecular weight of 900(20% by weight), 0.1% by weight of the polymer used in Example 4(Example 9) or Comparative Example 1 (Comparative Example 4) was added.The threshold load of the mixture was measured by means of a Falextester (V block: AISI-1137 free machining steel., Pin: SAE-3135 Ni-Crsteel, Surface roughness, maximum 10 micrometers (rms), Rotationalspeed: 290 rpm, Running speed: 9.8 cm/sec., Loading way: ratchet 360kg/min. (initial one minute), 135 kg/min. (subsequent one minute),Sample volume: 80 ml). Threshold load in Example 9 was 820 kg while thatin Comparative Example 4 was 590 kg.

The invention being thus described, it will be obvious that the same maybe varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the invention, and all suchmodifications as would be obvious to one skilled in the art are intendedto be included within the scope of the following claims.

What is claimed is:
 1. A fluorine-containing polymer comprising units ofthe formula: ##STR23## wherein R¹ and R² are, the same or different, agroup of the formula:

    R.sub.f (CH.sub.2).sub.n Y.sub.k --                        (II)

wherein R_(f) is a C₃ -C₂₁ fluorine-containing aliphatic group which maycontain at least one oxy group, Y is a group of the formula: ##STR24##wherein A is hydrogen or a lower acyl group, n is an integer of 0 to 8,k is 0 or 1; R³ and R⁴ are, the same or different, hydrogen or a loweracyl group, and Q¹ and Q² are, the same or different, a C₃ -C₁₂₀oxyalkylene group optionally having a hydroxyl group, or a group of theformula: ##STR25## wherein R⁵ is a C₃ -C₁₂₀ alkylene group optionallyhaving an oxy group or a C₆ -C₁₅ aromatic group and m is an integer of 1to 8; said polymer having a number average molecular weight of 5000 to100,000.
 2. A fluorine-containing polymer according to claim 1, whereinthe lower acyl group of R³ and R⁴ is one having 1 to 4 carbon atoms. 3.A fluorine-containing polymer according to claim 1, wherein Q¹ and Q²are a group of the formula: ##STR26## wherein R⁵ is a C₃ -C₁₂₀ alkylenegroup optionally having an oxy group or a C₆ -C₁₅ aromatic group, and mis an integer of 1 to
 8. 4. A fluorine-containing organic polymeraccording to claim 1, wherein Q₁ and Q₂ are each a C₃ -C₁₂₀ alkylenegroup.
 5. A fluorine-containing organic polymer according to claim 3,wherein R⁵ is a C₃ -C₁₂₀ alkylene group.
 6. A fluorine-containingorganic polymer according to claim 3, wherein R⁵ is a C₆ -C₁₅ aromaticgroup.
 7. A fluorine-containing organic polymer according to claim 3,wherein R⁵ is a C₃ -C₁₂₀ alkylene group having an oxy group.
 8. Afluorine-containing organic polymer according to claim 1, wherein Q₁ andQ₂ are each a C₃ -C₁₂₀ alkylene group having a hydroxy group.